CN102057066B - Recovery of rhenium - Google Patents
Recovery of rhenium Download PDFInfo
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- CN102057066B CN102057066B CN200980120663.4A CN200980120663A CN102057066B CN 102057066 B CN102057066 B CN 102057066B CN 200980120663 A CN200980120663 A CN 200980120663A CN 102057066 B CN102057066 B CN 102057066B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/1625—Leaching with acyclic or carbocyclic agents of a single type with amines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G47/00—Compounds of rhenium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to a method for recovering rhenium from an ethylene oxide catalyst containing rhenium and at least silver on a solid support, wherein at least a substantial portion of the rhenium present in the catalyst is extracted by intimate contact of the catalyst with one or more polar non-acidic organic solvents substantially free of water such that a rhenium-containing solution is formed containing the polar non-acidic organic solvent and extracted rhenium, the polar non-acidic organic solvent containing one or more oxygen, nitrogen, and/or halogen atoms in its molecular structure.
Description
Invention field
The rhenium-containing catalysts the present invention relates to from using reclaims rhenium value, particularly reclaims rhenium from the epoxyethane catalyst of rhenium-containing.
Background of invention
Rhenium is valuable, rare metal, and it has found a lot of subenvironments (niche) application.This metal is mainly used in being for example used for producing for example, in the petroleum reforming catalyzer (, bimetal Pt-Re composition) of high-octane rating hydrocarbon polymer and in the superalloy using in high-temperature turbine mechanism part at present.These two kinds of application represented be respectively estimated as rhenium end-use 20% and 60%.Rhenium is the hot strength character of some nickel class superalloys of known improvement also.
Rhenium is also day by day as containing silver on solid carrier as the promotor in the epoxyethane catalyst of active metal.These epoxyethane catalysts are on a large scale for the production of oxyethane, and it is the important as precursors of a lot of extensive commercial chemicals (for example, ethylene glycol) that use.Ethylene oxide catalyst typically contains up to about 0.5wt% rhenium, based on catalyst weight.Rare and the high price of considering rhenium, in these catalyzer, the amount of rhenium is sizable.The understanding more in detail of the epoxyethane catalyst of these rhenium-containings can be found in for example U.S. Patent number 4,766,105,4,808,738,4,820,675,5,364,826,4,829,044,5,418,202,5,739,075,5,545,603,5,663,385,5,739,075,5,801,259,5,929,259,6, in 372,925 and 6,368,998.
According to U.S.Geological Survey, Mineral Commodity, January2008, the price of rhenium reaches every kilogram 9,000 of every kilogram of in September, 7,000 and 2007 in every kilogram of in April, 5,000,2007 in January, 2007.At the beginning of 2008, the price of rhenium exceedes every kilogram of $ 10,000 marked prices.
The sharply rising of nearest high demand and price thereof for rhenium, it is necessary and useful making to reclaim rhenium.Therefore, paid special attention to seek improved for reclaiming the method for this precious metal.Referring to for example U.S. Patent number 2,967,757,3,260,658,3,348,942,3,407,127,3,458,277,3,798,305,3,862,292,3,855,385,3,733,388,3,932,579,4,185,078,4,049,771,3,244,475,4,278,641,4,521,381,4,557,906,4,572,823,4,599,153,4,599,223 and 7,166,145; U. S. application publication No. 2003/0119658,2007/0203351 and 2007/0227903; Foreign patent document GB 2 009 119A; And document Hydrometallurgy, 78 volumes, 3-4 phase, in August, 2005,166-171 page; Hydrometallurgy, 85 volumes, 1 phase, in January, 2007,17-23 page; And Ind.Eng.Chem.Res., volume 38 (5), 1999,1830-1836 page.
Most of above-mentioned prior aries all disclose separately or have made water extract rhenium from spent catalyzer and other rhenium-containing source with the form of the aqueous solution.Especially, the in the situation that of spent epoxyethane catalyst, make the main drawback of water be a lot of other metallic promoter agent along with rhenium together follow extraction.These other promotor typically comprise the element such as Li, Na, Cs, S, P, W, Ni, Hf, Ti, Zr and/or B.Therefore these other promotor that, the gained rhenium aqueous solution also can be measured by difference are polluted.
Because these other promotor need to be removed to reclaim pure rhenium, so typically need some additional steps with Separation of Rhenium.The selective adsorption of a kind of universal method that other element of rhenium and these is separated based on rhenium.The selective adsorption of rhenium is typically based on ion-exchange or carbon absorption.In the time using such as these adsorption technologies, before separating the rhenium reclaiming, need to leach the additional step of the rhenium adsorbing.These additional steps increase complicacy and the cost of the method, reduce the efficiency of the method simultaneously.In addition, along with number of steps in recovery method increases, rhenium loss is more, and it shows as the rate of recovery still less.
In addition, well-known and highly popular in prior art is not only to use the aqueous solution but also use strong acid that (for example, mineral acid is as HCl, HNO
3, H
2sO
4, chloroazotic acid, etc.) by spent rhenium-containing source dissolve and/or processing rhenium.As everyone knows, so sour corrodibility is very strong.Therefore, need to use specific equipment and treatment process.In addition, security consideration becomes subject matter.In addition, once requiring rhenium to separate with other component conventionally, the use of such strong acid just uses neutralization bases in acidization downstream.N-process often require in and the effective highly basic of strong acid or height causticity alkali.This feature further increases the demand for professional equipment and particular safety measure.Neutralizing treatment also produces more chemical wastes.Suitably process because refuse is essential, the generation of this chemical waste becomes another important financial burden.
From above-mentioned prior art investigation, there is the demand to the novel method for reclaiming rhenium, the method more simply (for example, needs still less step), more efficiently and still less expends.In the method also particularly advantageously, existing one or more to be typically used as other element of active catalytic metals or promotor in epoxyethane catalyst, is optionally for removing rhenium.
Invention summary
The invention provides improvedly for from rhenium-containing catalysts, particularly the epoxyethane catalyst of rhenium-containing reclaims the method for rhenium.Epoxyethane catalyst typically at least contains silver as additional elements.In catalyzer, silver typically remaines on solid carrier, typically on oxide carrier.
The inventive method comprises by catalyzer and one or more polar organic solvents, and the preferably close contact of the nonacid solvent of one or more polarity extracts at least major part from catalyzer and is present in the rhenium catalyzer, thereby forms rhenium-containing solution.Polarity (nonacid) organic solvent (herein also referred to as " solvent ") does not basically contain water, contains one or more oxygen, nitrogen and/or halogen atom in its molecular structure, and at least one, preferably until about six carbon atom.Rhenium-containing solution is containing the rhenium that is useful on the polar solvent in extraction and extracts.
Preferably, solvent extracts rhenium value by catalyzer in a selective manner, and the in fact all the components retaining except rhenium is not thus extracted.Also preferably described one or more solvents have fully low boiling point, and typically approximately 120 ℃ of left and right or lower, make follow-up evaporation easy.This makes it possible to more easily reclaim rhenium with strong solution or solid form, and also make can be more easily by solvent recycled simultaneously.
The epoxyethane catalyst that the present invention advantageously simplifies from using reclaims the technique of rhenium, and makes it more efficient.The method is simplified, this is because can save most of currently known methodss usually used in this field, for example ion-exchange and other absorption method, acid/alkaline purification, oxidation/distillation processing, corrodibility electrolytic process (caustic electrolytic method) and other.The method is more efficient, and this is because the method is preferably substantially extracted all rheniums in a selective manner in single step, and without additional processing and separating step.The method is also safer and still less expends, and this is because do not use caustic acid, and refuse is preferably minimized by the recirculation of solvent.
Detailed Description Of The Invention
The invention reside in the method by rhenium-containing catalysts selective recovery rhenium.Rhenium-containing catalysts can be any catalyzer as known in the art (wherein rhenium is on solid carrier).Rhenium can work in any appropriate manner, comprises for example as catalytic active substance or promotor.In special embodiment, rhenium-containing catalysts is ethylene oxide catalyst.Epoxyethane catalyst is any epoxyethane catalyst generally known in the art typically, and it at least contains silver as the catalytic active substance on solid carrier.
The carrier using in epoxyethane catalyst is generally solid refractory material.Carrier porous typically.Carrier can be by making such as the material of for example Alpha-alumina, activated carbon, float stone, magnesium oxide, zirconium white, titanium dioxide, diatomite, Fuller's earth, silicon carbide, silica, silicon carbide, clay, permutite, natural zeolite, silicon-dioxide and/or titanium dioxide, pottery and combination thereof.More typically, carrier is made up as silica or aluminum oxide of oxide material.Preferred carrier comprises having extreme high purity, for example Alpha-alumina of at least 95 % by weight purity.All the other compositions can comprise for example, the containing metal or containing nonmetallic other additive, promotor or impurity as silica, alkalimetal oxide (, sodium oxide) and trace of inorganic oxide except Alpha-alumina.
Epoxyethane catalyst typically contains the silver metal of catalytically effective amount, with catalysis by ethene and oxygen synthesize epoxyethane.Silver can be positioned on the surface of refractory support and/or spread all over the hole of refractory support.The silver of catalytically effective amount can be for for example until the silver in metal of approximately 45 % by weight, based on the gross weight of catalyzer that comprises carrier.Silver content as approximately 1% to approximately 40% take metal is more typical, and silver content is approximately 8% to approximately 35% to be also more typical, based on total catalyst weight.
In addition, typically comprise the basic metal of promotion amount at epoxyethane catalyst, or two or more alkali-metal mixtures, and/or the IIA family alkaline-earth metal of promotion amount, or the mixture of two or more IIA family alkaline-earth metal, and/or the main group element of promotion amount, or the mixture of two or more main group elements, and/or the transition metal of promotion amount or the mixture of two or more transition metal, and/or the rare earth metal of promotion amount or the mixture of two or more rare earth metals.All these promotor except basic metal can be any appropriate form, comprise for example zero-valent metal or high volence metal ion more.
Suitable alkali metal promoter comprises, for example lithium, sodium, potassium, rubidium, caesium or its combination.Caesium is normally preferred, and caesium and other alkali-metal combination are also preferred.Alkali-metal amount typically at about 10ppm within the scope of about 3000ppm, more typically at about 15ppm within the scope of about 2000ppm, more typically at about 20ppm within the scope of about 1500ppm, also more typically at about 50ppm within the scope of about 1000ppm, based on the weight of total catalyst, in basic metal.
Suitable alkaline-earth metal promotor comprises for example beryllium, magnesium, calcium, strontium and barium or its combination.The amount of alkaline-earth metal promotor is similarly to measure use with above-mentioned alkali metal promoter.
Suitable transition metal can comprise be for example selected from periodic table of elements IIIB family (scandium family), IVB family (titanium family), VB family (vanadium family), group vib (chromium family), VIIB family (manganese family), VIIIB family (iron, cobalt, nickel family), IB family (copper family) and IIB family (zinc family), with and combination element.More typically, transition metal is early transition metal, is selected from IIIB family, IVB family, VB family or group vib, for example hafnium, yttrium, molybdenum, tungsten, chromium, titanium, zirconium, vanadium, tantalum, niobium or its combination.
Typically, based on every gram of total catalyst, with approximately 0.1 micromole, to approximately 10 micromoles, more typically approximately 0.2 micromole is to approximately 5 micromoles for transition metal or rare earth metal promotor, and also more typically extremely approximately 4 micromolar amounts existence of approximately 0.5 micromole, in metal.
Suitable main group element comprises any element in IIIA family (boron family) to VIIA family (halogen family) in the periodic table of elements.For example, catalyzer can comprise one or more sulphur compounds, one or more phosphorus compounds, one or more boron compounds, one or more halogen-containing compounds or its combination of promotion amount.Catalyzer can also comprise main group element element form, except halogen.
Rare earth metal comprises any element with ordination number 57-103.Some examples of these elements comprise lanthanum (La), cerium (Ce) and samarium (Sm).
Rhenium component in catalyzer can be any appropriate form, but is more typically compound (for example, rhenium oxide) or the complex compound of one or more rhenium-containings.In epoxyethane catalyst, typically comprise rhenium to play the effect of promotor.Rhenium can exist with for example approximately 0.001 % by weight to the amount of approximately 1 % by weight.But more typically, rhenium is with approximately 0.005 % by weight for example to approximately 0.5 % by weight, and also more typically approximately 0.01 % by weight to the amount of approximately 0.05 % by weight exists, based on the weight of total catalyst that comprises carrier, in rhenium metal.
Typically, by the mistake (spent) for epoxyethane catalyst of this paper method processing.Term " spent " meaning is that catalyzer is no longer commercial useful, typically due to significantly reduced catalytic capability, selectivity or output.For example, if compared with live catalyst, selectivity of catalyst reduction exceedes 3%, can think that catalyzer is spent.More typically, if elective reduction exceedes 5%, think that catalyzer is spent.As another example, exceed 3 ℃ of productivity to keep initially providing as live catalyst if must make temperature of reaction raise, can think that catalyzer is spent.More typically, exceed 5 ℃ of productivity to keep initially providing as live catalyst if must make temperature of reaction raise, think that catalyzer is spent.
Alternately, catalyzer is not to use or spent, but because other reason need to be extracted rhenium.For example, may be because the rhenium-containing catalysts of abandoning in a large number appears in fill a prescription change or production program change.May expect that the catalyzer from abandoning extracts rhenium, and sell or use rhenium and other catalyst component of being extracted.
Epoxyethane catalyst can be any appropriate form, but is more typically applicable to the hollow cylinder form etc. of particle, piece, sheet, pill, ring, ball, wheel (wagonwheel) and the staggered subregion of fixed bed epoxidation reactor for size.Typically, carrier granule has at about 3mm within the scope of about 12mm, more typically at about 5mm to the equivalent diameter within the scope of about 10mm, this equivalent diameter conventionally with the internal diameter fit that the tubular reactor of catalyzer is wherein housed.Term " equivalent diameter " is for representing the size of irregular-shaped objects, and it is by have the size that represents this irregular-shaped objects with the mode of the diameter of the ball of irregular-shaped objects same volume.
In the method for the invention, by by catalyzer and one or more solvent close contacts, reclaim rhenium from epoxyethane catalyst.Take out (extract) preferably at least 30% from catalyzer, more preferably 40%, also more preferably at least 50% rhenium.Also more preferably, the rhenium that at least major part is present in catalyzer is extracted from catalyzer." major part " used herein typically looked like and referred at least about 85%, and more preferably from about 90%, more preferably at least about 95%, also more preferably taken out from catalyzer at least about 98% rhenium.Also more preferably, all rheniums are removed substantially, and this typically refers at least 99% rhenium and is taken out from catalyzer.
Can use the method for any close contact that is used to form solvent and catalyzer.Preferably, catalyzer is piece or the particle form of suitably dwindling, and it makes solvent can infiltrate and permeate relatively fast and easily all spaces and/or the hole of catalyzer.In order to accelerate this process or in order to improve rhenium alluvial, before extraction process or during, catalyzer can suitably grind, pulverizes, broken, powdered or minification otherwise.
Contacting also between solvent and catalyzer improved by the stirring that has comprised a kind of form during extraction process.Stir and also generally understand modification and recovery value.The suitable agitating method of some types for example comprise stir the mixture, shake mixture, by mixture bubbling, make mixture boiling and/or reversing, upset or rotate mixture in the container of uncovered or sealing or groove.
Herein for the solvent of this object owing to thering is one or more oxygen, nitrogen and/or halogen atom at its molecular structure but polarity.Term " organic solvent " meaning refers to that solvent contains at least one carbon atom in its molecular structure.Solvent can contain the carbon atom of any proper number, and can be any suitable molecular weight.Preferably, solvent contains and is no more than approximately 20 carbon atoms in its molecular structure, more preferably no more than approximately 12 carbon atoms, also more preferably until approximately 6 carbon atoms.More preferably, solvent contains until 4 carbon atoms.Solvent can comprise straight chain or branching, saturated or undersaturated, ring-type or acyclic part at its molecular structure.Unsaturated solvent can be aliphatic series or aromatics.
Solvent is preferably non-acid, and this is to reduce the selectivity of method because acidic chemical tends to by the extraction metal except rhenium.Acidic chemical also comprises some in other sour shortcoming of as above having discussed, as safety problem, need specific equipment and cause the generation of more refuses.
In one embodiment, solvent is alcohol.Suitably some examples of alcohol comprise methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, 2-amylalcohol, primary isoamyl alcohol, neopentyl alcohol, hexanol, vinyl carbinol, cyclopentanol, hexalin, and combination.
In the second embodiment, solvent is organic ester.Suitably some examples of organic ester comprise methyl-formiate, methyl acetate, ethyl acetate, ethyl formate, vinyl-acetic ester, methylcarbonate, ethyl lactate, ethylene carbonate, and combination.
In the 3rd embodiment, solvent is ketone.Suitably some examples of ketone comprise acetone, butanone (methyl ethyl ketone), ethyl nezukone, 2 pentanone, propione, cyclopentanone, methyl vinyl ketone, methyl ethyl diketone (2,4-diacetylmethane), and combination.
In the 4th embodiment, solvent is Organohalogen compounds.Described Organohalogen compounds can comprise any known halogenide, but are more preferably limited to the derivative of fluorine and chlorine.Suitably some examples of Organohalogen compounds comprise chloroform, methylene dichloride, tetracol phenixin, tetrachloroethylene, 1,1-ethylene dichloride, 1,2-ethylene dichloride, perchloro-hexane, tetrachloroethane, and combination.
In the 5th embodiment, solvent is amine.Suitably some examples of amine comprise ethamine, diethylamine, triethylamine, Isopropylamine, Diisopropylamine, diisopropyl ethyl amine, n-Butyl Amine 99, sec-butylamine, isobutylamine, TERTIARY BUTYL AMINE, piperidines, piperazine, quadrol, pyridine, tetramethyleneimine, diethylenetriamine, morpholine, and combination.
In the 6th embodiment, solvent is organophosphate.More preferably trialkylphosphate of described organophosphate.Some examples of suitable organophosphate comprise trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate isopropyl ester, tributyl phosphate, and combination.
In the 7th embodiment, solvent is ether.Suitably some examples of ether comprise diethyl ether, diisopropyl ether, two tertiary butyl ether, glycol dimethyl ether, furans, tetrahydrofuran (THF) ， diox, methyl tertiary butyl ether, 2-methyl cellosolve, cellosolvo, diglyme, butoxy ethanol, and combination.
In the 8th embodiment, solvent is acid amides.Suitably some examples of acid amides comprise methane amide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone (NMP), and combination.
In the 9th embodiment, solvent is nitrile.Suitably some examples of nitrile comprise acetonitrile, propionitrile, butyronitrile, and combination.
In the tenth embodiment, solvent is sulfoxide.The example of suitable sulfoxide comprises methyl-sulphoxide.
The solvent of other operable kind and type comprises that glycol (for example, ethylene glycol, propylene glycol), glycol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether), nitro solvent (for example, Nitromethane 99Min., nitroethane), aldehyde solvent (for example, furfural), tetramethylene sulfone (sulfolane), urea solvent (for example, 1, 3-dimethyl-3, 4, 5, 6-tetrahydrochysene-2 (1H)-pyrimidone (DMPU)), boric acid ester solvent (for example, trimethyl borate, triethyl borate), hexamethyl phosphoric triamide (hexamethylphosporamide) (HMPA), and ionic liquid.
Can also use any combination of above-mentioned solvent.For example, can preferably use the combination of alcohol and ketone, or the combination of alcohol and ether, or the combination of ether and ketone, etc.Some embodiments can comprise for example following combination: ethanol and acetone, methyl alcohol and acetone, acetone and methyl ethyl ketone, or ethanol and methyl ethyl ketone.
In the present invention, preferably use the solvent (dry solvent) that does not basically contain water, contain at most the solvent of trace water.When reason is for this reason extraction, the existence of water increases the possibility of extracting the element except rhenium from spent catalyzer.Trace water can be for being for example no more than 5 % by weight water in solvent.More preferably, water-content is less than 1 % by weight, is also more preferably less than 0.5 % by weight water, is also more preferably less than 0.1 % by weight water.
Can be in normal condition, under room temperature and normal pressure, use solvent to carry out extraction process.Room temperature is greatly in the temperature range of 15-32 ℃, and normal pressure is approximately 1 normal atmosphere.Alternately, extraction process can be carried out at higher or lower temperature or under higher or lower pressure.For example, have in lower boiling situation at solvent, may expect that during milking cooling and/or pressurized solvent is to keep it as liquid.For thering is high boiling solvent, expect if remove solvent, may expect heated solvent and/or reduce pressure, to increase alluvial and/or to allow solvent more easily to evaporate.
Extraction process can be carried out under standard air, or alternately under the atmosphere changing, carries out.The atmosphere changing can be for example atmosphere of enriched in oxygen more or less.The oxygen not too atmosphere of enrichment can provide as hydrogen, nitrogen, argon or carbonic acid gas by for example comprising other gas.
Preferably, solvent extracts rhenium in a selective manner from spent catalyzer.More preferably, remove rhenium in the mode of high selectivity.The method of high selectivity, by substantially removing rhenium value completely from catalyzer, retains great majority or all other chemical substances (being pollutent) simultaneously and is not substantially removed (not extracted from catalyzer) and is confirmed.Some possible pollutents comprise silver for example, basic metal, alkaline-earth metal, transition metal, main group element and rare earth metal except rhenium.Above-mentioned lower alcohol, ester and ketone are particularly preferred for from spent ethylene oxide catalyst selective recovery rhenium.
For silver, described extraction process should be at least a little optionally aspect removal rhenium.More preferably described extraction process is high selectivity for removing rhenium, retains all silver substantially simultaneously and is not removed.Extraction process is also preferably with respect to a class or multiclass basic metal and/or alkaline-earth metal selective removal rhenium, and/or with respect to a class or multiclass main group element selective removal rhenium, and/or with respect to a class or multiclass transition metal selective removal rhenium, and/or with respect to a class or multiclass rare earth metal selective removal rhenium.
Preferred described extraction process can extract at least 30,40 or 50% rhenium value, and one or more pollution substances of at least 80%, more preferably 90%, more preferably at least 95% keep not extracted from catalyzer simultaneously.More preferably, at least 80%, more preferably 90%, more preferably 95%, also more preferably at least 98% rhenium value is extracted, and simultaneously at least 80%, more preferably 90%, also more preferably at least 95% pollution substance retains not from catalyzed dose of extraction.Also more preferably, at least 98%, more preferably 99% rhenium value is extracted, and the while at least 98%, more preferably the reservation of 99% pollution substance is not extracted.Most preferably, with respect to all other chemical species that exist in catalyzer, rhenium is selectively removed as mentioned above.
Extract and produce rhenium-containing solution.Generally need to utilize certain by the separate mode of gained solution and catalyst solid material separation.As required, can be for this purpose after extracting or during use filtration.Alternately, can during extraction process, make carrier or other solid keep separating with solution, make not need follow-up filtration.Some approach that can realize this purpose for example comprise during milking in netted or semipermeable film and hold spent catalyzer, or settle solids material is together with removing top layer solvent, such as by decant or by supplementing or overflowing solvent.
Can also use continuous extraction process.For example, can utilize the adverse current of washing soln to combine with spent moving-bed of catalyst.In addition, solvent can be by using, reclaim and then using and recirculation continuously in extraction process.
In one embodiment, solvent is by utilizing Soxhlet extraction device to be used and recirculation continuously.In Soxhlet extraction device, spent catalyzer is placed in open container, and open container is placed in the encloses container that extracts solvent is housed.Make to extract solvent evaporation by heating.The solvent condenses of evaporation enters in open container, and starts to extract rhenium from catalyzer.Along with continuing evaporation and condensation, the solvent in the container of containing catalyst is full of.Once be full of, the solvent that contains rhenium can be sucked out or transfer in larger container, therein spent solvent is evaporated again to also condensation and is back in the container that holds spent catalyzer.In this way, fresh solvent continuous supplementation is removed solvent from open container, and the rhenium-containing solution being simultaneously held in outside vessel becomes denseer.Circulation can repeat the number of times of any expectation, for example 5,10 or 20 circulations.
The rhenium-containing solution obtaining by extraction process can be used as it is, and does not need further processing.But, more possibly, need further processing to make the more applicable end product of doing of rhenium.For example, preferably that rhenium solution is concentrated.Can use any currently known methods for concentrated solution.Comprise by for example heating and/or reduction vaporization part solution for the preferred method of concentrated solution.Can also adopt by other method as selective solvent absorption or ultrafiltration process removal solvent.Can also preferably substantially get on except all solvents are to provide solid rhenium product from rhenium-containing solution.
Use the method for evaporating of heating and/or vacuum generally more preferably for removing a part of solvent.Therefore,, in order to make evaporation technology easier, preferred solvent has under approximately 1 atmospheric standard pressure and is no more than the boiling point of 120 ℃.Also more preferably, solvent has under approximately 1 atmospheric standard pressure and is no more than the boiling point of 100 ℃.Above-mentioned lower alcohol, ester and ketone, particularly have those that are no more than four carbon atom, is particularly preferred, and this is because they generally have the boiling point lower than other solvent.
In preferred embodiments, most of solvent through evaporation is recovered.After catalyzer is processed by aforesaid method, significantly the solvent of share can be contained in the hole of catalyzer.Equally highly useful is to be recovered in the solvent of holding back in moist catalysis.Therefore, expection herein is not only reclaimed solvent from gained rhenium solution, and reclaims the solvent that moist catalysis inside holds.Recovered solvent can advantageously recycle in extraction process.The recovery and reuse of solvent advantageously reduce refuse, therefore reduce costs, and also reduced solvent vapour is disposed to the negative environmental consequences in atmosphere simultaneously.
The recovery and reuse of solvent are provided by continuous extraction process in preferred embodiments.Extraction process can for example be used Soxhlet extraction device continuously.In Soxhlet extraction device, spent catalyzer is placed in open container, and open container is placed in the encloses container that extracts solvent is housed.Make to extract solvent evaporation by heating.Evaporating solvent condensation enters in open container, and starts to extract rhenium from catalyzer.Along with continuing evaporation and condensation, the solvent in the container of containing catalyst is full of.Once be full of, rhenium-containing solvent can be sucked out or transfer in larger container, therein spent solvent is evaporated again to also condensation and is back in the container that holds spent catalyzer.In this way, fresh solvent continuous supplementation is removed solvent from open container, and the rhenium-containing solution simultaneously remaining in outside vessel becomes denseer.Circulation can repeat the number of times of any expectation, for example 5,10 or 20 circulations.
Can carry out other working method or chemical reaction to rhenium solution, to manufacture the end product of available rhenium-containing.For example, metal chelator, precipitation agent, polymkeric substance or other material can be added into solution, to cause the precipitation of for example rhenium compound.Rhenium compound can be for example rhenium-chelate complexes, and rhenium-polymer complex, or rhenium material, for example, as the oxide compound of rhenium, sulfide, halogenide, rhenium complex ion (, silicate, carbonate, nitrate radical, wolframate radical).Alternately, can be by for example chilling of solution (chilled), heating, electrolysis (for example, in order to produce rhenium metal or metal alloy), allow place under given conditions for some time be exposed to oxygenant or reductive agent under, as a part for the method for the rhenium-containing end product for the production of suitable.
Rhenium-containing end product can be introduced for the production of any other requirement the end product of rhenium.For example, thus obtained rhenium is as the initial soln from extraction process or can for example, for the treatment of catalyst precursor (, support of the catalyst) through the solution regulating, and to mix therein rhenium, thereby produces the live catalyst of rhenium-containing.Preferably consider that the catalyzer for regenerating is epoxyethane catalyst herein.About the regeneration of epoxyethane catalyst, resistivity against fire carrier can be flooded by any methods known in the art and mix with rhenium and the silver-colored promotor together with any expectation.Dipping method is described in for example U.S. Patent number 4,761,394,4,766,105,4,908,343,5,057,481,5,187,140,5,102,848,5,011,807,, in 5,099,041 and 5,407,888, the method for impregnated carrier described herein is by reference to being incorporated herein.In addition can utilize, any known predeposition, codeposition and the rear deposition process of various promotor.
Rhenium-containing end product can also be for example rhenium-metal alloy.For example, rhenium can be for the preparation of platinum-rhenium catalyst, and it is for the processing of gasoline and hydrocarbon.Rhenium can also be for the preparation of to filament and the useful tungsten-rhenium alloy of thermopair.Rhenium can also be as the additive in nickel class superalloy, and described nickel class superalloy is for the manufacture of turbine blade and gas turbine.Further aspect of the present invention is to use one or more organic solvents that do not basically contain water, the preferably catalyst recovery rhenium of the nonacid organic solvent of one or more polarity that contain one or more oxygen, nitrogen and/or halogen atom in its molecular structure from containing rhenium at solid carrier.As mentioned above, the solvent that contains one or more oxygen, nitrogen and/or halogen atom in its molecular structure is considered to " polarity " solvent.
The object of following embodiment is to further illustrate the present invention.Scope of the present invention is never limited to embodiment described in literary composition.
In the following embodiments, spent catalyzer is the epoxyethane catalyst that has been used the prolonged period.The silver that described catalyzer contains catalytically effective amount on low surface area carrier, also contains rhenium, caesium, lithium, tungsten and sulphur.Catalyzer, as for example United States Patent(USP) Nos. 4,766,105,4,808,738,4,820,675 and 5,364, is prepared described in 826.
Comparative examples A
Use art methods
In standard laboratory container, 50 parts of spent catalyzer are at room temperature dipped in 100 parts of water.Use little pump around catalyst pellet's circulation 2 hours in water.Extracting while finishing, by the aqueous solution and catalyst separating and analyze its content.
Comparative example B
Use the method for prior art
Repeat the method identical with Comparative examples A, difference is by using small-sized immersion heater and temperature regulator that water temperature is remained on to 80 ℃.
Embodiment 1
Use ethanol (EtOH) to extract rhenium
Repeat the method identical with Comparative examples A, difference is to use ethanol to replace water.
Embodiment 2,3,4
Extract rhenium with ethanol, change extraction time simultaneously
Repeat the method identical with embodiment 1, difference is, for embodiment 2,3 and 4, extraction time is reduced to respectively 60,30 and 15 minutes.Analytical results is summarized in table 1, in the percentage ratio of the element from catalyzer extraction.
As shown in table 1, the water extracting method of Comparative examples A demonstrates rhenium extraction and is worth approximately 93%.But the amount of caesium (Cs), tungsten (W), lithium (Li) and the sulphur (S) of contaminative is quite large, particularly sulphur is extracted into solution from catalyzer completely.Shown at comparative example B, pollutent extracted amount is along with Aquo System temperature raises and increases.Thus, art methods demonstrates for the height of rhenium non-selective, therefore, is unacceptable for the object of the invention.
Embodiments of the invention 1 use ethanol to replace water.Comparative examples A and B and the embodiment 1 use equivalent time of 2 hours extract.But contrary with Comparative examples A and B, effective extraction (approximately 78%) that embodiment 1 demonstrates rhenium combines with the extraction of the obvious reduction of pollutent.For example, table 1 demonstrates, and in embodiment 1, uses ethanol, and caesium value is reduced to 6.9% from 55.0%, and tungsten value is reduced to 0% from 28.9%, and lithium value is reduced to 10% from 60.5%, and sulfur number is reduced to 0% from 100%.Compared with Comparative examples A, the pollutent value in embodiment 1 is only for 12.5%, 0%, 16.5% and 0% of the analog value shown in Comparative examples A.
Carry out embodiment 2 in the mode identical with embodiment 1 with ethanol, difference is that time quantum reduces half to 60 minute.As described in Example 2, the amount of the rhenium of extraction is reduced to 54.7%, but the amount of the pollutent extracting even further reduces than embodiment 1.
Also carry out embodiment 3 and 4 in the mode identical with embodiment 1 with ethanol, difference is that time quantum is reduced to respectively 30 and 15 minutes.As shown, use ethanol further reduce extraction time also cause lower rhenium extraction value together with reduce pollutent extraction value.
Embodiment 5
Use ethanol to extract continuously
In the present embodiment, extract continuously rhenium value with Soxhlet extraction device.25 parts of spent catalyzer are placed in to extraction cup, 90 parts of ethanol are placed in and extract flask.Heated solvent is until it comes to life, and vapour condensation also refluxes above spent catalyzer.In the time of the full solvent of catalyzer cup, load has the solvent of rhenium value of dissolving sucked back to flask (boilingflask).Extract and continue approximately 1 hour.During this period, there are 7 complete extraction circulations.Before the flask of the material that contains solvent and the be extracted constituent content that they are extracted in analysis, be cooled to room temperature.
Embodiment 6
Use Virahol (iPrOH) to extract rhenium
Repeat the method for embodiment 5, difference is that ethanol is replaced by Virahol.
Embodiment 7
Extract rhenium with acetone
Repeat the method for embodiment 5, difference is that ethanol is replaced by acetone.
Embodiment 8
Use methyl ethyl ketone (MEK) to extract rhenium
Repeat the method for embodiment 5, difference is that ethanol is replaced by methyl ethyl ketone.
The results are summarized in table 2 of extracting method in embodiment 5-8, in the percentage ratio of the element that is extracted from catalyzer.As shown in table 2, embodiment 5 and 7 demonstrate major part or substantially all rhenium be extracted, retain major part or all contaminants matter is not extracted simultaneously.Embodiment 6 and 8 demonstrates the lower rhenium rate of recovery, but the pollution substance extracted amount reducing.
Table 2
Embodiment 9
Use the rhenium impregnation catalyst agent carrier reclaiming
Repeat described in embodiment 7, difference is to extract solution and is placed in water distilling apparatus.Make acetone solvent evaporation, until be only left 4.6 parts in flask.Contain all rheniums that extract from spent catalyzer through concentrated solution.This solution is added in a flask, the Ag that this flask contains 29% silver oxalate/quadrol complex form and containing caesium, containing lithium, tungstenic and sulfocompound.Mixture is used as dipping solution to prepare fresh high-selectivity catalyst.Initial stage pickling process known in the art (incipient impregnation method), for flooding alpha-alumina supports, is then calcined.Calculate the concentration of different additive (comprising rhenium) in dipping solution, with the catalyst composition that obtains expecting after calcining.Catalyzer, as high selectivity catalyzer, is issued to 91% selectivity in its peak performance.
Although shown and described the content of thinking at present the preferred embodiment of the invention; but one skilled in the art will recognize that; can there be other and further embodiment in the case of not departing from described in this application spirit and scope of the invention; the application comprises all such improvement, and it is in the protection domain described in this paper claims.
Claims (22)
1. for the method from the catalyst recovery rhenium that contains rhenium at solid carrier, the method comprises by the close contact of catalyzer and the nonacid organic solvent of one or more polarity, extract at least most of rhenium from catalyzer, make to form the rhenium-containing solution of the rhenium that contains the nonacid organic solvent of described polarity and be extracted, the nonacid organic solvent of wherein said polarity contains one or more oxygen in its molecular structure, nitrogen and/or halogen atom, wherein said catalyzer contains rhenium and at least contains silver on solid carrier, the nonacid organic solvent of described polarity contains at most trace water, trace water for being no more than 5 % by weight water in solvent.
2. method according to claim 1, the nonacid organic solvent of wherein said one or more polarity is selected from alcohol, organic ester, ketone, Organohalogen compounds, amine, organophosphate, ether, acid amides and nitrile.
3. method according to claim 1, the nonacid organic solvent of wherein said one or more polarity is selected from alcohol, ester and ketone.
4. method according to claim 1, the nonacid organic solvent of wherein said polarity is ethanol.
5. method according to claim 1, the nonacid organic solvent of wherein said polarity is Virahol.
6. method according to claim 1, the nonacid organic solvent of wherein said polarity is acetone.
7. method according to claim 1, the nonacid organic solvent of wherein said polarity is methyl ethyl ketone.
8. according to the method described in any one in claim 1 to 7, wherein during milking, heat the nonacid organic solvent of described polarity.
9. method according to claim 1, it further comprises that the part by removing the nonacid organic solvent of polarity concentrates rhenium-containing solution.
10. method according to claim 1, it further comprises that the mode wherein contained rhenium is converted into solid form processes rhenium-containing solution.
11. methods according to claim 10, wherein obtain the rhenium that reclaims of solid form by substantially removing the nonacid organic solvent of the polarity of rhenium-containing solution.
12. methods according to claim 1, wherein, with respect to silver, the nonacid organic solvent of described polarity from catalyst selectivity remove rhenium.
13. methods according to claim 1, wherein said catalyzer further contains a class or multiclass basic metal and/or alkaline-earth metal.
14. methods according to claim 13, wherein, with respect to silver and a class or multiclass basic metal and/or alkaline-earth metal, the nonacid organic solvent of described polarity is optionally removed rhenium.
15. methods according to claim 13, wherein said catalyzer further contains a class or multiclass and is selected from periodictable IIIA family to the main group element of VIIA family, and/or is selected from the early transition metal element of periodictable IIIB family-group vib.
16. methods according to claim 15, wherein, with respect to silver, a class or multiclass basic metal and a class or multiclass main group element and/or early transition metal element, described polar organic solvent is optionally removed rhenium.
17. methods according to claim 1, it further comprises the end product that uses rhenium-containing solution to produce rhenium-containing.
18. methods according to claim 17, wherein the end product of rhenium-containing is rhenium compound.
19. methods according to claim 17, wherein the end product of rhenium-containing is rhenium-containing catalysts.
20. methods according to claim 19, wherein rhenium-containing catalysts is the epoxyethane catalyst of rhenium-containing.
21. methods according to claim 1, it further comprises continuous extraction process, wherein, by solvent evaporation the condensation in the hole from rhenium-containing solution and/or treated catalyzer, so that the solvent through recirculation to be provided, this solvent through recirculation is used further to the extraction of rhenium.
22. one or more organic solvents are used for the purposes of the catalyst recovery rhenium from containing rhenium at solid carrier, described one or more organic solvents are the nonacid organic solvents of one or more polarity that contain one or more oxygen, nitrogen and/or halogen atom in its molecular structure, and wherein said catalyzer contains rhenium and at least contains silver on solid carrier.
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| US12/115,779 US7763096B2 (en) | 2008-05-06 | 2008-05-06 | Recovery of rhenium |
| PCT/EP2009/003242 WO2009135665A1 (en) | 2008-05-06 | 2009-05-06 | Recovery of rhenium |
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| EP (1) | EP2285994B1 (en) |
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2008
- 2008-05-06 US US12/115,779 patent/US7763096B2/en active Active
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2009
- 2009-05-05 TW TW98114852A patent/TW201005102A/en unknown
- 2009-05-06 WO PCT/EP2009/003242 patent/WO2009135665A1/en active Application Filing
- 2009-05-06 CN CN200980120663.4A patent/CN102057066B/en not_active Expired - Fee Related
- 2009-05-06 EP EP09741884.2A patent/EP2285994B1/en not_active Not-in-force
- 2009-05-06 JP JP2011507831A patent/JP2011523437A/en not_active Ceased
- 2009-05-06 RU RU2010145307/02A patent/RU2478721C2/en not_active IP Right Cessation
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| TW201005102A (en) | 2010-02-01 |
| RU2010145307A (en) | 2012-06-20 |
| RU2478721C2 (en) | 2013-04-10 |
| EP2285994A1 (en) | 2011-02-23 |
| US20090277305A1 (en) | 2009-11-12 |
| JP2011523437A (en) | 2011-08-11 |
| EP2285994B1 (en) | 2015-06-10 |
| US7763096B2 (en) | 2010-07-27 |
| WO2009135665A1 (en) | 2009-11-12 |
| CN102057066A (en) | 2011-05-11 |
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